石墨烯及其衍生物的分散改性及其在防腐涂料中作用机制的研究进展

樊小根; 吴思; 李惠霞; 夏宇正; 石淑先

doi:10.13801/j.cnki.fhclxb.20201214.003

石墨烯及其衍生物的分散改性及其在防腐涂料中作用机制的研究进展

doi: 10.13801/j.cnki.fhclxb.20201214.003

北京化工大学　材料科学与工程学院，北京 100029

基金项目: 北京化工大学-中日友好医院生物医学转化工程研究中心联合项目(XK2020-13)

详细信息

通讯作者:
石淑先，博士，副教授，硕士生导师，研究方向为功能高分子材料　 E-mail：shisx@mail.buct.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2020-10-16
- 录用日期: 2020-12-04
- 网络出版日期: 2020-12-14
- 刊出日期: 2021-08-15

Research progress of dispersion modification and anticorrosion mechanism of graphene and its derivatives in coatings

College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

摘要

摘要: 石墨烯(Gr)具有优异的光学、电学和力学等特性，在材料、能源或生物医学领域具有重要的应用前景，特别是Gr具有超隔离性，当将其用作涂料填料使用时，可极大提高涂层的防腐性能。但是由于Gr的高比表面积及层间的范德华力，又使其非常容易团聚，限制了其实际使用。对Gr进行分散改性，促进其在基体中的均匀分布，对扩大Gr的应用范围和提高材料的性能具有重要意义。本文主要介绍了Gr及其衍生物的共价改性、非共价改性、掺杂改性和原位聚合改性等方法，通过增加Gr层间位阻效应，改变Gr表面的双亲性，增强其与涂料聚合物基之间的相容性，从而提高其在涂料中的分散性。此外，本文还分析了各种改性方法的优缺点，提出了进一步提高Gr及其衍生物分散性的改性方向；总结了Gr及其衍生物在防腐涂料中的作用机制，建议今后在实验探索的基础上，加强对防腐机制的研究。
- 石墨烯及其衍生物 /
- 分散改性 /
- 相容性 /
- 涂料 /
- 防腐性能
Abstract: Graphene (Gr) has excellent properties such as super-isolation, super-hydrophobicity and super-high specific surface area, making it a revolutionary material for improving the anticorrosion performance of coatings in the 21st century. However, it is easy to agglomerate due to the Van Der Waals force and the high specific surface area between Gr layers, which limits its application in the anti-corrosion coatings. The dispersion modification of Gr can promote its uniform distribution in the coating, which is of great significance to improve the anticorrosive properties of the coating. This paper introduces the structural characteristics of Gr and the anticorrosion mechanism of Gr in coatings, and summarizes the methods of Gr dispersion modification, including the covalent modification of Gr with the small organic molecules, the organic polymers and the inorganic nanoparticles, the non-covalent modification of Gr through the π-π interaction, the hydrogen bonding and the ionic bonding, doping Gr to introduce the new elements and giving it excellent performance, and through the in-situ polymerization to improve the compatibility between Gr and polymer. According to the dispersion principles such as increasing the interlayer steric hindrance of Gr, changing the amphiphilicity of its surface and increasing its compatibility with the polymer, the dispersibility of Gr can be improved remarkable. The uniformly distributed Gr forms a hydrophobic network in the coating, which can effectively improve the corrosion resistance of the coating and expand the application range of the coating. In addition, the paper also analyzed the advantages and disadvantages of various modification methods, and proposed a research direction to further improve the dispersion of Gr and its derivatives; summarized the mechanism of Gr and its derivatives in anti-corrosion coatings, and suggested to strengthen the research on the anti-corrosion mechanism based on experimental exploration in the future.
- graphene and its derivatives /
- dispersion modification /
- compatibility /
- coatings /
- anticorrosive properties

HTML全文

图 1 石墨烯(Gr)、氧化石墨烯(GO)和还原氧化石墨烯(RGO)的示意图

Figure 1. Schematic diagram of graphene oxide (GO) and reduced graphene oxide (RGO) derivation from graphene (Gr)

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图 2 Gr及其衍生物的分散改性方法总结示意图

Figure 2. Summary of dispersion methods of Gr and its derivatives

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图 3 γ-氨丙基三甲氧基硅烷(APTMS)-GO/环氧树脂 (EP)涂料合成原理示意图

Figure 3. Schematic diagram of the synthesis principle of γ-aminopropyl trimethoxysilane (APTES)-GO/epoxy (EP) coating

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图 4 TiO₂-GO的合成反应工艺图

Figure 4. Synthetic reaction process diagram of TiO₂-GO

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图 5 N掺杂石墨烯的制备示意图

Figure 5. Schematic diagram of the preparation of N-doped graphene derivatives

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图 6 原子转移自由基聚合(ATRP)法合成GO-g-聚甲基丙烯酸甲酯(PMMA)的示意图

Figure 6. Schematic of the synthesis route of GO-g-polymethyl methacrylate (PMMA) by atom transfer radical polymerization (ATRP)

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图 7 Gr在涂层中的物理屏蔽作用示意图

Figure 7. Schematic diagram of the physical shielding effect of Gr in the coating

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图 8 Gr在涂层中的化学保护作用示意图

Figure 8. Schematic diagram of the electrochemical protection of Gr in the coating

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表 1 Gr及其衍生物的分散改性方法总结

Table 1. Summary of dispersion modification methods of Gr derivatives

Modification method		Modified materials	Modified group	Principle of dispersion	References
Covalent modification	Organic small molecules	Silane coupling agenttitanate coupling agent	—OH, —COOH, epoxy group	Steric hindrance, compatibility	[24-31]
		Organic amines	—COOH, epoxy group	Compatibility, amphipathic	[32-35]
		Isocyanates	—OH, —COOH, epoxy group	Compatibility	[36-38]
	Organic polymer	PVP, PANI, PEI, PEG, PCD, Polyisocyanate	—OH，—COOH, epoxy group	Compatibility, amphipathic	[39-44]
	Inorganic nanoparticles	SiO₂, TiO₂, Si₃N₄, CaCO₃, Al₂O₃	—OH, —COOH, epoxy group	Steric hindrance	[45-53]
Non-covalent modification	π-π interaction	Aniline trimer, PDA, PPy, PANI, P₂BA, PAT, PGHEP, lignin, TP, BN, GO	Six-membered carbon ring	Steric hindrance	[32, 54-64]
	Ionic bond	IPDI, CTAB, DA	—OH, —COOH, epoxy group	Steric hindrance, compatibility	[65-67]
	Hydrogen bond	PPy, ATP, PANI	—OH, —COOH, epoxy group	Amphipathic, steric hindrance	[68-70]
Doping modification		3 amino-1,2,4-triazole, PA	—	Steric hindrance	[71-72]
In-situ polymerization		ACAT, NABM, ABA	—COOH, epoxy group, six-membered carbon ring	Compatibility	[73-75]
Notes: PVP—Polyvinylpyrrolidone; PANI—Polyaniline; PEI—Polyethyleneimine; PEG—Polyethylene glycol; PCD—Polycarbodiimide; P₂BA—Poly(2-butylaniline); PPy—Polypyrrole; PAT—Poly(2-aminothiazole); TP—Tea polyphenol; PGHEP—Hydroxy epoxy phosphate monomer; DA—Dopareine; ATP—Attapulgite; ACAT—Amino-terminated aniline trimer; NABM—N-(2-aminoethyl)-2-bromo-2-methylpropanamide; PA—Phytic acid; ABA—4-aminobenzoic acid.

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